JP2020531713A - Membrane-forming dispersion and sizing dispersion - Google Patents

Abstract

The present invention relates to a film-forming dispersion containing a functionalized polyamide and water.

Description

The present invention relates to film-forming dispersions and sizing dispersions containing functionalized polyamides and water, preferably applied on carbon fibers.

Thermoplastic composites are essentially thermoplastic resin matrices (eg, polyamide (PA), polypropylene (PP), polybutylene terephthalate (PBT), polycarbonate (PC), polyphenylsulfide (PPS), polyetheretherketone. (PEEK), polyetherimide (PEI), etc.) and reinforcing fibers (eg, glass fiber, carbon fiber, aramid fiber, etc.). Reinforcing fibers may be short fibers, long fibers or continuous fibers, allowing the use of thermoplastic composites in structural applications with high loads. The fiber-resin matrix interface is where the load is transferred from the resin matrix to the fibers.

The fibers are typically coated with a film-forming composition or sizing agent, which will generally be pulled out of the bush and applied to the surface of the fibers. By sizing or film formation, the fiber processability is improved and the fiber can be handled, while on the other hand, the interfacial strength is improved, which has a strong influence on the mechanical properties of the finally obtained composite material. The sizing or film-forming composition typically comprises several components having different functions. Specifically, a film forming agent (a polymer-based water emulsion / dispersion having different chemical properties capable of forming a film during fiber processing) and a coupling agent for a sizing composition (mainly a bond between a resin matrix and a reinforcing fiber). Ingredients such as silanes, lubricants, antistatic agents, pH regulators, and cross-linking agents that affect

Among the thermoplastic composite materials, composite materials using a polyamide resin matrix, for example, composite materials using PA6, PA66, and PA12 are important representative examples in the market. Composites using a polyamide resin matrix are particularly suitable for applications that require high temperature resistance and excellent hydrolysis resistance. Currently, most of the film-forming compositions and sizing compositions used in polyamide fiber-reinforced thermoplastic composites are polyurethane (PU) film-forming agents of various properties (aliphatic, blocked, crosslinked polyurethane, etc.). based on. The polyurethane film forming agent enables relatively good fiber treatment and imparts compatibility between the polyamide resin matrix and the reinforcing fibers. However, they do not have much high temperature resistance. After applying a film-forming or sizing agent to the fibers, the fibers are typically heated. The fibers may be stored before the liquid resin is applied during compounding. The melting point of some resins is quite high. For example, nylon 66 has a temperature of about 268 ° C, and PPS has a temperature of about 285 ° C. Therefore, the formed film or sizing needs to be able to withstand high temperatures sufficiently. High temperature decomposition of the film and sizing at high temperatures result in defects in the film, defects during sizing, and defects at the fiber-resin matrix interface, which reduces the mechanical properties of the composite. There is a risk.

In order to obtain a dispersion in which the polymer is dispersed in water (hereinafter referred to as "polymer aqueous dispersion"), preferably an organic solvent-free polymer aqueous dispersion, to be suitable for fiber sizing or film-forming applications. It is preferable to have the important properties of:
-The polymer exhibits good compatibility / affinity with water and good polarity, and is stable over time without causing sedimentation, aggregation, flocculation, etc. in water;
Properties for fiber sizing or film formation, especially on glass-reinforced fibers:
The polymer aqueous dispersion has good stability when mixed with silanes (eg aminosilanes, epoxysilanes) in sizing formulations and does not precipitate, settle, etc. for at least 72 hours; and / or. The color of the polymer is white or slightly yellow and does not affect the color of the final polymer aqueous dispersion; the dispersion that darkens when applied to fibers (eg glass fiber) is the final Affects the appearance of the product (dark fiberglass is typically unacceptable on the market).

When using amine-functionalized polyamides in the absence of solvents, it may not be possible to obtain stable polyamide aqueous dispersions due to polymer / water compatibility issues. When the polyamide is functionalized with maleic anhydride, the color of the modified polymer (ie, the final aqueous dispersion) is dark. This is unacceptable for use in the application of forming films on glass fibers or in sizing of glass fibers, especially when transparent or light-colored resins are used.

The present invention solves one or more of the above problems. A preferred embodiment of the present invention solves one or more of the above other problems. More specifically, the present invention can improve high temperature resistance. A (favorable) aspect of one point of view is also a (favorable) aspect of another point of view.

From one point of view, the present invention relates to a film-forming dispersion containing a functionalized polyamide and water, wherein the functionalized polyamide is a carboxyl compound functionalized polyamide and / or a sulfonated compound functionalized polyamide. Polyamides are characterized by reacting at least partially with one or more neutralizers in the presence of water.

In some preferred embodiments, the solids content of the film-forming dispersion is at least 10% by weight and up to 60% by weight, preferably at least 15% by weight and up to 50% by weight, and more preferably at least 20% by weight and up to 50% by weight. 45% by weight, even more preferably at least 25% by weight and up to 40% by weight, most preferably at least 30% by weight and up to 35% by weight. The solid content is determined according to ISO3251 (2008).

In some preferred embodiments, the solid content of the film-forming dispersion comprises a functionalized polymer, and the content of the functionalized polymer relative to the total solid content of the film-forming dispersion is at least 31% by weight, preferably at least 35% by weight. %, More preferably at least 50% by weight, even more preferably at least 45% by weight, even more preferably at least 75% by weight, and most preferably at least 90% by weight.

In some preferred embodiments, the film-forming dispersion comprises a neutralizing agent, which neutralizing agent is preferably a base, more preferably from amines, preferably secondary, tertiary or quaternary amines. Selected from the group of For example, it is preferably selected from the group consisting of diethylethanolamine or trimethylamine, diethanolamine, and / or inorganic hydroxides (eg sodium hydroxide or potassium hydroxide).

In some preferred embodiments, the neutralizing agent has a neutralization ratio of 75% to 1000%, preferably 90% to 750%, preferably 100% to 750% relative to the amount of acid functionality of the functionalized polyamide. , More preferably 100% to 400%, even more preferably 100% to 300%, and most preferably 100% to 200%.

In some preferred embodiments, the functionalized polymer is functionalized with one or more linear dicarboxylic acids, preferably with a linear dicarboxylic acid selected from the group consisting of adipic acid, sebacic acid and isophthalic acid. Will be done.

In some preferred embodiments, the sulfonated compound comprises at least (2) carboxyl groups and at least (1) sulfonate groups, preferably aromatic moieties, more preferably dicarboxybenzenesulfonates. , More preferably 3,5-dicarboxybenzene sulfonate, most preferably sodium 3,5-dicarboxybenzene sulfonate.

In some preferred embodiments, the functionalized polyamide has an acid value of 10-100 (mgKOH) / g as measured by potentiometric titration according to ISO2114 (2000).

In some preferred embodiments, the average particle size of the dispersed particles in the dispersion is determined by laser scattering in distilled water and is at least 5 nm and at most 1000 nm.

In some embodiments, the film-forming dispersion is a dispersion in which particles in the liquid are dispersed.
In some preferred embodiments, the film-forming dispersion further comprises 1-20% by weight of the nonionic surfactant, more preferably 3-15% by weight, even more preferred, based on the weight of the functionalized polyamide. Contains 4-12% by weight, most preferably 5-10% by weight.

In some preferred embodiments, the film-forming dispersion is essentially catalyst-free and / or essentially solvent-free (other than water).

In some preferred embodiments, the weight loss of the functionalized polyamide is 15% or less, more preferably 10% or less, even more preferably 8% or less. Such weight loss is determined by thermogravimetric analysis at 350 ° C. in an air atmosphere in a closed oven by heating with 15 mg of functionalized polyamide as a starting material at 50 ° C. to 400 ° C. for 70 minutes.

From one point of view, the present invention relates to a sizing dispersion, which comprises the following components.
A film-forming dispersion according to an embodiment of the present invention; and a silane, preferably a silane selected from the group consisting of aminosilanes, epoxysilanes, or mixtures thereof, preferably aminosilanes.

In one aspect, the invention is a fiber, preferably a carbon fiber treated with a film-forming dispersion according to an embodiment of the invention or a sizing dispersion according to an embodiment of the invention;
And a composition comprising a resin, preferably a thermoplastic resin.

In one respect, the present invention relates to a method of producing a fiber reinforced resin product, which method comprises the following steps:
The process of providing fibers, preferably carbon fibers;
A step of treating the fibers with a film-forming dispersion according to an embodiment of the present invention or a sizing dispersion according to an embodiment of the present invention to obtain treated fibers; and applying a resin to the treated fibers. Process to do.

In one aspect, the invention is a fiber reinforced product comprising fibers, preferably carbon fibers treated with a film-forming dispersion according to an embodiment of the invention or a sizing dispersion according to an embodiment of the invention; Regarding.

In some embodiments, the present invention relates to the use of a film-forming dispersion as described above as a film-forming agent on fibers, preferably carbon fibers.

Prior to discussing the units and methods of the invention, it is understood that the invention is not limited to the particular units and methods or combinations described below. Such units and methods and combinations can of course be modified. It should also be understood that the terms used herein are not intended to be limiting, as the scope of the invention is limited only by the appended claims.

As used herein, the singular forms "a," "an," and "the" include both the singular and plural forms, unless the context explicitly indicates otherwise. The term "comprising" is used herein as "comprises," and the term "comprised of" as used herein is "including," "includes," or "containing," "contains." It is synonymous. And these terms are inclusive or open-ended, do not exclude additions, and do not exclude non-limiting elements, requirements or steps of method. As used herein, the terms "comprising," "comprise," and "comprised of" are "consisting of," "consists," and It is understood to include the term "consists of".

The description of the numerical range by endpoint includes all numbers and fractions contained within each range as well as the listed endpoints. The term "one or more" or "at least one", such as one or more or at least one member (s) of a group of members, is clear in itself, but by further illustration, the term is In particular, reference to any of the members, or any one of the members, or any two or more members of the member, eg, any one of the members. One or more members, or any two or more of the members (eg, three or more, four or more, five or more, six or more, or seven or more, etc.), and all numbers of the members. Includes references to.

All references cited herein are hereby incorporated by reference in their entirety. In particular, the teachings of all references herein are incorporated herein by reference.

Unless otherwise defined, all terms used in the disclosure of the present invention include technical and scientific terms, but have meanings generally understood by those skilled in the art to which the present invention belongs. .. With further guidance, definitions of terms are included to better understand the teachings of the present invention.

The following sections define different aspects of the invention in more detail. Each aspect defined in this way can be combined with any other aspect, unless the opposite is explicitly stated. In particular, any feature that is shown to be preferred or advantageous can be combined with any other one or more features that are shown to be preferred or advantageous. Throughout the specification, "an embodiment" or "one embodiment" includes certain features, structures, or properties described in connection with an embodiment in at least one embodiment of the invention. Means that. Therefore, the appearance of the phrase "in one embodiment" or "in one embodiment" in various places throughout the specification does not necessarily refer to the same embodiment. Moreover, certain features, structures, or properties can be combined in any suitable manner in one or more embodiments, as will be apparent to those skilled in the art from this disclosure. Moreover, although the embodiments described herein include some other features that are included in other embodiments, the combination of features of different embodiments will be appreciated by those skilled in the art. It is within the scope of the invention and means forming different embodiments. For example, in the appended claims, any of the claimed embodiments can be used in any combination.

The parenthesized and / or bold reference numbers attached to each element are not intended to limit each element, they merely exemplify the elements. It should be understood that other embodiments can be utilized and structural or logical changes can be made without departing from the scope of the invention. Therefore, the following detailed description should not be construed in a limited sense and the scope of the invention is defined by the appended claims.

In one aspect, the present invention is a film-forming dispersion containing a functionalized polyamide and water, wherein the functionalized polyamide is a polyamide functionalized with a carboxyl compound and / or a polyamide functionalized with a sulfonate compound. The present invention relates to a film-forming dispersion, wherein the functionalized polyamide reacts with at least one or more neutralizing agents in the presence of water. Preferably, the functionalized polyamide is at least 31% by weight, preferably at least 35% by weight, more preferably at least 50% by weight, even more preferably at least 45% by weight, based on the total solid content of the film-forming dispersion. %, More preferably at least 75% by weight, most preferably at least 90% by weight.

In some embodiments, the present invention relates to a film-forming dispersion comprising a functionalized polyamide and water, wherein the functionalized polyamide is a polyamide functionalized with a carboxyl compound and / or a polyamide functionalized with a sulfonate compound. The functionalized polyamide is at least partially reacted with one or more neutralizing agents in the presence of water, and the solid content of the film-forming dispersion is preferably 10% by weight to 60% by weight. It is more preferably 15% by weight to 50% by weight, more preferably 20% by weight to 45% by weight, even more preferably 25% by weight to 40% by weight, and most preferably 30% by weight to 35% by weight. The solid content is determined according to ISO3251 (2008).

The term "dispersion" refers to a dispersion in which individual particles of (one) material are dispersed in a continuous phase of another material. Preferably, the continuous phase is a liquid, more preferably the continuous phase comprises water. More preferably, at least 75% by weight of the continuous phase is water, even more preferably at least 90% by weight of water, and most preferably at least 95% by weight of water. In some embodiments, the dispersion is a dispersion in which the particles, in their individual state, are suspended in a continuous aqueous phase.

In some embodiments, the particle size of the solid particles in the film-forming dispersion is at least 1 nanometer, more preferably at least 5 nanometers, even more preferably at least 10 nanometers, even more preferably at least 25 nanometers. Meters, most preferably at least 50 nanometers.

In some embodiments, the particle size of the solid particles in the film-forming dispersion is at most 10,000 nanometers, more preferably up to 1000 nanometers, even more preferably up to 750 nanometers, even more preferably up to 500 nanometers. Meters, most preferably 250 nanometers at most.

In some embodiments, the particle size of the solid particles in the film-forming dispersion is at least 1 to 10000 nanometers, more preferably at least 5 to 1000 nanometers, and even more preferably at least 10 to 750 nanometers. Meters, even more preferably at least 25-up to 500 nanometers, most preferably at least 50-up to 250 nanometers.

The present invention also relates to a method for preparing a film-forming dispersion containing a functionalized polyamide and water, which method comprises the following steps:
-The step of functionalizing the polyamide with a carboxyl compound and / or a sulfonate compound; and
A step of reacting the functionalized polyamide with one or more neutralizers at least partially in the presence of water is included. The step of reacting the functionalized polyamide with the neutralizing agent at least partially is also referred to as a neutralization step or a neutralization reaction.

The present inventors have found that such a film-forming dispersion and a preferred embodiment thereof have significantly improved heat resistance as compared with the current commercially available polyurethane film-forming agents. This is shown by the results of thermogravimetric analysis TGA. As illustrated in the Examples section, the weight loss obtained with a commercially available polyurethane film forming agent under the same test conditions is 25-30%, whereas the weight loss obtained with a polyamide film forming agent is 25 to 30%. The resulting weight loss at 350 ° C. in the air environment is less than 15%.

In some preferred embodiments, the film-forming dispersion comprises a neutralizing agent capable of at least partially neutralizing the acid groups of the functionalized polyamide. Preferably the neutralizing agent is a base, and more preferred neutralizing agents are amines, preferably secondary, tertiary or quaternary amines such as diethylethanolamine (DEEA), trimethylamine (TMA), triethylamine (TEA), diethanolamine. (DEA) or a mixture thereof is selected from the group. More preferably, it is diethylethanolamine (DEEA) or triethylamine (TEA), the most preferred neutralizer is triethylamine (TEA), and / or an inorganic hydroxide such as sodium hydroxide or potassium hydroxide. The present inventors have found that such a neutralizing agent enables stable dispersion of functionalized polyamide in water. The listed neutralizers can also impart very high heat resistance to the water dispersion of the functionalized polyamide. Moreover, such neutralizers can at the same time impart very good stability to the optionally present silanes in the dispersion.

In some preferred embodiments, the neutralizing agent has a neutralization ratio of at least 75% or more and 1000% or less, preferably 100% or more and 750% or less, more preferably 100, as compared to the amount of acid functional groups in the functionalized polyamide. % Or more and 300% or less, more preferably 102% or more and 500% or less, still more preferably 102% or more and 200% or less. It is more preferably at least 104% by weight to 400% by weight, further preferably 104% by weight to 200% by weight, most preferably 105% by weight to 200% by weight, still more preferably 105% by weight to 120% by weight. As used herein, the term "neutralization ratio" refers to the amount of base functional groups (moles) used in the neutralization reaction to the amount of acid functional groups (represented in molars) present in the functionalized polyamide. (Represented by). Preferably, the neutralization ratio is determined by amine valence determination according to TM5253. Such a neutralization ratio itself provides good water dispersion stability of the polyamide and is used in combination with a coupling agent, preferably silane.

In some embodiments, the neutralizing agent is diethyl ethanolamine (DEEA), with a neutralization ratio of preferably 75-200%, more preferably 100% -200%, even more preferably 100% -175. %, Even more preferably 102% to 150%, even more preferably 104% to 125%, most preferably about 105%.

In some embodiments, the neutralizing agent is triethylamine (TEA), with a neutralization ratio of preferably 100% to 600%, more preferably 100% to 500%, even more preferably 100% to 400%. For example, at least 200% to 600%, for example 250% to 500%, for example at least 300% to 450%, for example about 400%.

In some embodiments, the neutralizing agent is:
Diethylethanolamine (DEEA), preferably with a neutralization ratio of 75-200%, more preferably 100% -200%, even more preferably 100% -175%, even more preferably 102% -150%, even more. It is preferably 104% to 125%, most preferably about 105%; and / or triethylamine (TEA), preferably having a neutralization ratio of 100% to 600%, more preferably 100% to 500%, even more preferably. It is 100% to 400%, most preferably 200% to 400%, for example 200% to 600%, for example 250% to 500%, for example 300% to 450%, for example about 400%.

In some embodiments, the acid-functionalized polyamide reacts with the neutralizer even in the absence of a catalyst.

In some embodiments, the film-forming dispersion is expressed as a percentage of the total weight of the film-forming dispersion, at most 20% by weight, preferably 15% by weight or less, more preferably 10% by weight or less, even more. It is preferably 8% by weight or less, most preferably 6% by weight or less, and contains a functionalized polyamide.

In some embodiments, the film-forming dispersion is at least 1% by weight, preferably 2% by weight or more, more preferably 3% by weight or more, more preferably 3% by weight or more, in terms of weight% of total weight of the film-forming dispersion. Contains 4% by weight or more, most preferably 5% by weight or more of functionalized polyamide.

In some preferred embodiments, the film-forming dispersion is characterized in that the content of the functionalized polyamide is in the range of at least 1% by weight or more and 20% by weight or less. The content of the functionalized polyamide is preferably 2% by weight to 15% by weight, more preferably 3% by weight to 10% by weight, even more preferably 4% by weight to 8% by weight, and most preferably 5% by weight to 6% by weight. %. A film-forming dispersion containing a functionalized polyamide at such a content can be applied with an accurate amount of film-forming agent on the fiber when used for applications that provide good processing and / or mechanical properties.

In some embodiments, the functionalized polyamide has a number average molecular weight (Mn) of at least 2000 Da to a maximum of 15000 Da, more preferably 2000 Da to 8000 Da, and most preferably 2000 Da to 5000 Da. Preferably, the number average molecular weight (Mn) is determined by gel permeation chromatography by dissolving the functionalized polyamide in a suitable solvent (eg, hexafluoroisopropanol) and preferably comparing it with a monodisperse polystyrene standard. Such a range imparts good workability and / or good heat resistance.

In some embodiments, at least (one) terminal of the functionalized polyamide is a carboxylic acid group, more preferably both ends of the functionalized polyamide are carboxylic acid groups. The carboxylic acid group imparts surface activity to the neutralized functionalized polyamide. This is necessary for forming a film on the fiber surface in sizing. The surface active properties also provide good compatibility with water and / or can stably disperse the polyamide.

In some preferred embodiments, the functionalized polyamide is a functionalized aliphatic polyamide. Alternatively, in another embodiment, the functionalized polyamide is a functionalized aromatic polyamide. In particular, the functionalized aromatic polyamide can impart excellent hydrolysis resistance.

The functionalized polyamide is a polyamide functionalized with a carboxyl compound and / or a polyamide functionalized with a sulfonate compound. In some preferred embodiments, the functionalized polymer is functionalized with a linear dicarboxylic acid. Preferred linear dicarboxylic acids are selected from the group consisting of adipic acid, sebacic acid and isophthalic acid. When the carboxylic acid compound is a linear dicarboxylic acid, the present inventors have that the color of the functionalized polyamide and / or the color remaining on the fiber after film formation and / or sizing is slightly pale yellowish white. I found.

In some embodiments, the polyamide (preferably containing a bifunctional amine) is reacted with a dicarboxylic acid in the presence of water. The final acid functionality is determined by the excess acid equivalent used. Excess carboxylic acid groups preferably provide good water affinity after neutralization.

In some embodiments, the functionalized polymer (functionalized polyamide) may be functionalized with a non-linear carboxylic acid such as isophthalic acid. However, this can affect the color of the film-forming dispersion and / or the color that remains on the fibers after sizing.

In some embodiments, the functionalized polymer comprises at least (one) polyamide moiety, which is functionalized with an acid functional group, preferably a dicarboxylic acid functional group, preferably via an amide bond. , Covalently bonded to the repeating unit atom of the at least (one) polyamide moiety. The term "polyamide moiety" can refer to the moiety of a polymer backbone in which different monomers are attached to each other by an amide bond.

In some preferred embodiments, the sulfonate compound comprises at least (2) carboxyl groups and at least (1) sulfonate groups. Preferably, the sulfonate compound contains an aromatic moiety, more preferably dicarboxybenzene sulfonate, even more preferably 3,5-dicarboxybenzene sulfonate, most preferably sodium 3,5-dicarboxybenzene sulfonate. It is salt.

The sulfonate groups in the functionalized polyamide impart appropriate polarity / water affinity to the polymer, which can provide a stable aqueous dispersion with properties suitable for film forming and / or sizing applications for fibers.

In some embodiments, the functionalized polyamide is at least 10 (mgKOH) / g, preferably 15 (mgKOH) / g or more, more preferably 20 (mgKOH) / g or more, prior to contact with the neutralizer. Even more preferably, it has an acid value of 30 (mgKOH) / g or more, and most preferably 45 (mgKOH) / g. The acid value is measured by the potentiometric titration method according to ISO2114 (2000).

In some embodiments, the functionalized polyamide is 100 (mgKOH) / g or less, preferably 75 (mgKOH) / g or less, more preferably 60 (mgKOH) / g or less, prior to contact with the neutralizer. It is more preferably 55 (mgKOH) / g or less, and most preferably 50 (mgKOH) / g or less. The acid value was measured by the potentiometric titration method according to ISO2114 (2000).

In some preferred embodiments, the functionalized polyamide is characterized by having an acid value of 10 (mgKOH) / g or more and 100 (mgKOH) / g or less prior to contact with the neutralizing agent. The acid value is preferably 15 (mgKOH) / g to 75 (mgKOH) / g, more preferably 20 (mgKOH) / g to 60 (mgKOH) / g, and even more preferably 30 (mgKOH) / g to 55 / mgKOH. ) / G, most preferably 45 (mgKOH) / g to 50 (mgKOH) / g. The acid value is measured by the potentiometric titration method according to ISO2114 (2000). Such an acid value can enhance the long-term stability of the polyamide aqueous dispersion, preferably in combination with a coupling agent (preferably silane). The stability of the dispersion is determined according to the SB108 test method. Such an acid value can also affect the molecular weight of the functionalized polyamide.

In some preferred embodiments, the average particle size of the dispersed particles in the dispersion is at least 5 nm or more and 1000 nm or less, preferably 8 nm or more and 800 nm or less, more preferably 10 nm or more and 500 nm or less, still more preferably 20 nm or more and 300 nm or less, most preferably. It is preferably 30 nm or more and 200 nm or less. Such particle size positively affects long-term dispersion stability. The particle size is preferably measured according to the TM5151 test method.

In some preferred embodiments, the membrane-forming dispersion further comprises a nonionic surfactant. In some preferred embodiments, the film-forming dispersion comprises at least 1% by weight and up to 20% by weight, more preferably at least 3% to 15% by weight, and most preferably 5% by weight of the nonionic surfactant. Includes% to 10% by weight.

In some preferred embodiments, the nonionic surfactant is selected from the group consisting of ethoxylated castor oil, alkoxylated ethylenediamine or block copolymers of ethylene oxide and propylene oxide. It is preferably a copolymer of triblock ethylene oxide and propylene oxide.

In some preferred embodiments, the film-forming dispersion contains the nonionic surfactant at least 1% by weight and up to 20% by weight, more preferably 3% to 15% by weight, based on the functionalized polyamide. Most preferably, it contains 5% by weight to 10% by weight. The nonionic surfactant is selected from the group consisting of polyester containing castor oil, ethoxylated castor oil, alkoxylated ethylenediamine, and / or block copolymers containing ethylene oxide and propylene oxide.

The present inventors have found that such a nonionic surfactant further contributes to the heat resistance of the dispersion. Such a nonionic surfactant enables control of the viscosity of the dispersion. Preferably, the viscosity of the dispersion at 25 ° C. is 1 × 10 ^-4 Pa · s to 5.0 Pa · s, preferably 1 × 10 ^-3 Pa · s to 3.5 Pa · s, more preferably 1 × 10. ^-2 Pa · s ~ 2.5 Pa · s.

In some preferred embodiments, the film-forming dispersion is essentially catalyst-free and / or essentially free of solvents other than water. In some embodiments, the film-forming dispersion is essentially free of zinc and / or tin catalysts such as dibutyltin dilaurate. In some embodiments, the membrane-forming dispersion is essentially free of acetone and / or 1-methoxy-2-propanol.

The phrase "the composition is essentially free of certain compounds" is used in the composition as an impurity contained in the starting material or as a residue after the purification step to specifically remove the compound. It means that it does not contain compounds other than the unavoidable impurities found in.

In some preferred embodiments, the weight loss of the functionalized polyamide is up to 15%, preferably 10% or less, more preferably 8% or less. The weight loss of the functionalized polyamide is determined by thermogravimetric analysis at 350 ° C. in an air atmosphere in a closed oven and is 50 ° C. to 400 ° C. starting from 10-15 mg functionalized polyamide, preferably 15 mg functionalized polyamide. It is a weight loss when heated for 70 minutes.

In some embodiments, the solids content of the film-forming dispersion is at least 10% by weight and up to 60% by weight, preferably 15% to 50% by weight, more preferably 20% to 45% by weight. Even more preferably, it is 25% by weight to 40% by weight, and most preferably 30% by weight to 35% by weight. The solids content is determined according to ISO3251 (2008). It was observed that the thermal stability of the film-forming composition and / or the sizing dispersion can be increased by setting such a solid content, and in particular, the film-forming composition has thermal stability even at a high temperature such as 350 ° C.

In some preferred embodiments, the ratio of the functionalized polymer to the total solid content of the film-forming dispersion is at least 31% by weight, preferably 35% by weight or more, more preferably 50% by weight or more, even more preferably 45. By weight or more, even more preferably 75% by weight or more, most preferably at least 90% by weight or more. In particular, with respect to the high temperature resistance of the film formed by the film-forming dispersion, it is beneficial that the proportion of the functionalized polymer in the solids in the dispersion is high. High proportions of other solids, such as surfactants and / or non-functional polymers, may not contribute to high temperature resistance or, in severe cases, reduce high temperature resistance.

In some embodiments, the solids content of the film-forming dispersion is at least 10% by weight and at most 60% by weight, preferably 15% to 50% by weight, more preferably 20% to 45% by weight. Even more preferably, it is 25% by weight to 40% by weight, and most preferably 30% by weight to 35% by weight. The solids content is determined according to ISO3251 (2008). It has been observed that such a solid content improves the thermal stability of the film-forming composition and / or the sizing dispersion at a high temperature such as 350 ° C. The ratio of the functionalized polymer to the total solid content of the film-forming dispersion is preferably at least 35% by weight, more preferably 50% by weight or more, still more preferably 45% by weight or more, still more preferably 75% by weight or more. Most preferably, it is 90% by weight or more.

In some embodiments, the film-forming dispersion has a solids content of at least 10% and up to 60%. The solids content is determined according to ISO3251 (2008). It was observed that such a solid content ratio can enhance the thermal stability of the film-forming composition and / or the sizing dispersion, and particularly has thermal stability even at a high temperature such as 350 ° C. The ratio of the functionalized polymer to the total weight of the solid content of the film-forming dispersion is preferably at least 35% by weight, more preferably 50% by weight or more, still more preferably 45% by weight or more, still more preferably 75% by weight. By weight or more, most preferably 90% by weight or more.

In some embodiments, the solids content of the film-forming dispersion is at least 10% by weight and up to 60% by weight, preferably 15% to 50% by weight, more preferably 20% to 45% by weight, and even more. It is more preferably 25% by weight to 40% by weight, and most preferably 30% by weight to 35% by weight. The solid content is determined according to ISO3251 (2008). With such a solid content, the thermal stability of the film-forming composition and / or the sizing dispersion can be enhanced, particularly at high temperatures such as 350 ° C. Then, at least 35% by weight of the solid content of the film-forming dispersion liquid is the functionalized polymer with respect to the total weight of the solid content of the film-forming dispersion liquid.

In some embodiments, the solids content of the film-forming dispersion is at least 10% by weight, 60% by weight, preferably 15% to 50% by weight, more preferably 20% to 45% by weight, even more preferably. Is 25% by weight to 40% by weight, most preferably 30% by weight to 35% by weight. The solids content is determined according to ISO3251 (2008). It was observed that such a solids content improved the thermal stability of the film-forming composition and / or the sizing dispersion at high temperatures such as 350 ° C. Assuming that the total solid content of the film-forming dispersion is 100% by weight, at least 50% by weight of the solid content of the film-forming dispersion is the functionalized polymer.

In some embodiments, the film-forming dispersion can be used directly as a sizing dispersion for carbon fibers.

In one aspect, the invention contains the following components, especially with respect to sizing dispersions for glass fibers.
Membrane-forming dispersion according to an embodiment of the present invention;
Silanes are preferably selected from the group consisting of aminosilanes such as γ-aminopropyltriethoxysilane, epoxysilanes such as [3- (2,3-epoxypropoxy) propyl] trimethoxysilanes, or mixtures thereof. Aminosilane.

Silanes typically act as a coupling agent. A coupling agent that provides a chemical bond between a fiber reinforcing material, particularly a glass fiber reinforcing material and a resin matrix. The silane preferably provides the required chemical compatibility with the thermoplastic resin matrix.

The composition of one embodiment is a carbon fiber treated with a fiber, preferably a film-forming dispersion according to an embodiment of the present invention or a sizing dispersion according to an embodiment of the present invention; and a resin, preferably a thermoplastic. It is a composition containing a resin.
The resin is preferably not the above-mentioned functionalized polyamide.

In certain preferred embodiments, the resin is a thermoplastic resin. Preferred thermoplastic resins are acrylic resin, acrylonitrile butadiene styrene resin (ABS), polyamide resin (nylon or aramid), polylactic acid resin (PLA), polybenzoimidazole resin, polycarbonate resin, polyether sulfone resin, polyether ether ketone resin. , Polyetherimide resin, polyethylene resin, polyphenylene oxide resin, polyphenylene sulfide resin, polypropylene resin, polystyrene resin, polyvinyl chloride resin, and polytetrafluoroethylene resin (PTFE or Teflon (registered trademark)). It is preferably a thermoplastic resin. In a more preferred embodiment, the resin is polyamide, preferably nylon or aramid, more preferably selected from the group consisting of PA6, PA66, PA12, PA6 / 66 or PA66 / 610, most preferably PA6, PA66, Selected from the group consisting of PA6 / 66.

In some preferred embodiments, the fibers are selected from the group comprising glass fibers, carbon fibers, aramid fibers and natural fibers, preferably the fibers are glass fibers and / or carbon fibers.

In some embodiments, the fibers are carbon fibers, including graphite fibers. In some embodiments, the carbon fibers are pitch carbon fibers, rayon carbon fibers, or PAN (polyacrylonitrile) carbon fibers.

In some embodiments, the carbon fibers may be twisted carbon fibers, untwisted carbon fibers and / or never twisted carbon fibers.

In some embodiments, the fibers, especially carbon fibers, may be bundles of filaments, preferably each bundle comprising at least 10 and up to 100,000 filaments. It is more preferably 100 to 80,000 filaments, even more preferably 500 to 60,000 filaments, and most preferably 1000 to 50,000 filaments.

In some embodiments, the fiber may be a sheet or woven fabric, which may be a woven fabric, a non-woven fabric or a unidirectional sheet. The sizing of the film formation of the fibers can be performed before or after the fibers are made into a cloth or sheet.

In one aspect, the present invention relates to a method for forming a fiber, preferably a carbon fiber reinforced resin product, which method comprises the following steps:
The process of providing fibers, preferably carbon fibers;
A step of treating the fiber with a film-forming dispersion according to an embodiment of the present invention or a sizing dispersion according to an embodiment of the present invention to obtain the treated fiber;
A step of applying a resin to the treated fiber.

In some embodiments, treating the fibers with a film-forming dispersion or a sizing dispersion involves contacting the fibers with the dispersion and subsequently drying the fibers, preferably the dispersion. It is done by evaporating water from. Preferably, the dispersion is applied to the fibers using a roll coater, preferably a kiss roll coater.

In some embodiments, applying the resin to the treated fibers is a compounding of the treated fibers with the resin, preferably in a melt blender or extruder, more preferably in an extruder. Including compounding.

One aspect of the present invention relates to a fiber reinforced article, wherein the fiber reinforced article is carbon treated with fibers, preferably a film-forming dispersion according to an embodiment of the invention or a sizing dispersion according to one embodiment of the invention. Fiber; and resin.

In some embodiments, the fiber reinforced article is used in applications that require high temperature resistance and good hydrolysis resistance. In some embodiments, the fiber reinforced article is selected from the group including:
・ For automobiles, articles placed under the hood
・ Semi-structural and structural automobile articles
-Electrical and electronic applications (eg connectors)
・ Equipment
・ Sporting goods and / or
・ Gears and bearings

In one aspect of the invention, a film-forming dispersion as described above as a film-forming agent on fibers, preferably carbon fibers (also referred to herein as a film former). Regarding the use of liquid. In some preferred embodiments, the film-forming agent is solvent-free. In some embodiments, the film-forming agent is used in fiber-reinforced thermoplastic composites, most specifically for sizing compositions of polyamide-based composites. Membrane-forming agents overcome most of the limitations of current sizing formulations based on polyurethane film-forming agents, which have limited high temperature and hydrolysis resistance.

The film-forming agent dispersion can be used as the only film-forming agent in the final sizing composition, or has different chemical properties such as polyurethane, epoxy, epoxy-ester and / or epoxy-urethane. It can be used as the main film-forming agent in combination with other co-film formers.

Preferably, the thickness of the film is at least 10 nm and up to 500 nm, more preferably 30 nm to 400 nm, more preferably 50 nm to 300 nm, still more preferably 70 nm to 200 nm, most preferably 90 nm to 150 nm or less, still more preferably about 100 nm. is there.

In order to illustrate the properties, advantages and features of the present invention in more detail, some preferred embodiments will be disclosed as examples. Therefore, the present invention discloses many embodiments and modifications that will be understood by those skilled in the art, and the scope of the present invention is not limited to the exemplary examples shown below.

The following test method was used in the examples. These test methods are also preferred test methods for obtaining relevant parameters.

Acid value determination
The acid value represented as a mgKOH / g sample was obtained by potentiometric titration according to ISO2114 (2000).

Determination of amine value (TM5253)
The content of amine groups represented as meqNH ₂ / g or mgKOH / g samples was determined by the potentiometric titration method described below.

A predetermined amount of material is weighed in a beaker, the material is dissolved in a solvent (eg methanol) and when the material is completely dissolved, a titration solution (eg HBr in acetic acid (0.05N)) is added and automated. Potentiometric titration is performed using a dosing device (eg, Titrino PLUS 818 manufactured by Metrohm).

Amine value (meqNH ₂ / g) = (V * NHBr) / m
Amine value (meqKOH / g) = Amine value (meqNH ₂ / g) * PEKOH
V: Volume of HBr required to reach the equivalence point (ml)
N HBr: Normality of HBr solution
m: Amount of material (g)
PE KOH: KOH equivalent (56.1 g / eq)

Thermogravimetric analysis (TGA)
This method was used to determine the weight loss of a material in a particular temperature range in a nitrogen or air environment, as described below.

Typical instruments used for these measurements are METTLER TOLEDO's METTLER TG50, METTLER M3 and METTLER TC10A / TC15 TA controllers.
A predetermined amount of dry material is weighed in a crucible and then the material is heated by a heating lamp in a closed oven to a desired temperature value under nitrogen or air flow. The machine-created graphs are then synthesized to have weight loss at a particular temperature.

In this specific example, 10 to 15 mg of a dry film-forming dispersion was used, and the temperature was raised from 50 ° C. to 400 ° C. over 70 minutes in an air atmosphere.

Table 1A shows the weight loss of the dispersions as various dry film forming agents at various temperatures.

Comparative Examples 1 to 6 mean a dry film-forming dispersion (without silane). Comparative Examples 1 to 6 refer to a standard polyurethane film-forming agent, and the product of the present invention refers to a film-forming dispersion according to an embodiment of the present invention, as shown in Table 1B.

A comparative example is a commercially available product.
Comparative Example 1: Neoxil 9851 (Aliancys);
Comparative Example 2: Neoxil 9851HF (Aliancys);
Comparative Example 3: Neoxil 8200A (Aliancys);
Comparative Example 4: Neoxil 8200A HF (Aliancys);
Comparative Example 5: Baybond PU405 (Covestro);
Comparative Example 6: Baybond PU407 (Covestro)

Particle size distribution analysis (TM5178)
This method was used to determine the average diameter of particles in a nanometer-represented dispersion using the laser scattering method, as described below.

The droplets of the dispersion are added to the distilled water in the water distilled twice and mixed until the solution becomes uniform. The solution was then poured into a cuvette and placed on a particle size analyzer (eg, Beckman-Coulter N5 instrument).

The average particle size is expressed in nanometers and the particle size distribution profile is expressed as "single peak" or "two peaks".

Stability of the dispersion itself (TM5151)
This method is used to determine the temporal stability of polymer dispersion in water, as described below.

The dispersion was filtered and poured into a closed container. The material is visually checked monthly to assess its appearance for separation, agglomeration and sedimentation.

Key dispersion properties are also measured and their values are compared to the original at the time of manufacture, for example for particle size.

Appearance of dispersion (TM2265)
This method evaluates the appearance of polymer dispersion in water by qualitatively expressing it as follows.

Color: Evaluation of the color of the material, eg, white, yellow, etc. Transparency: Evaluation of the transparency of the material, eg, transparent, cloudy, cloudy, etc. Contamination: If contaminated, there was contamination Only if case described Uniformity: Assess material homogeneity
Properties: Evaluate the properties of materials, such as liquids, crystals, powders, etc.

Stability of dispersion with silane (SB108) This method is at least between a polymer dispersion in water and a silane compound with different chemistries (typically used in fiber sizing compositions). It was adopted to determine stability / compatibility for 72 hours (3 days).

The ratio of the polymer dispersion in water to the silane compound (eg, aminosilane or epoxysilane) is calculated and adjusted. The solids content of the final formulation is adjusted in a plastic beaker prior to preparing the mixture.

Testing with Aminosilane Aminosilane is added to water under stirring conditions for at least 10 minutes (hydrolysis of silane). The calculated amount of aqueous polymer dispersion is then added to the hydrolyzed aminosilane with stirring for at least 10 minutes.
Pour the mixture into a closed plastic container and leave it there. The stability over time (whether there is separation, aggregation, sedimentation, etc.) is evaluated by visual observation.
The main dispersion characteristics are also measured and their values (eg particle size) are compared to the original values at the time of manufacture.

Testing with Epoxysilane Epoxysilane is added to the polymeric aqueous dispersion with stirring for at least 45 minutes. Water is then added to the epoxy-silane / polymer aqueous dispersion mixture with stirring for at least 10 minutes.
The mixture is poured into a closed plastic container and left there. The stability over time (whether there is separation, aggregation, sedimentation, etc.) is evaluated by visual observation.
The main dispersion properties are also measured and their values (eg particle size) are compared to the original values at the time of manufacture.

Table 2 shows various properties of various film-forming dispersions. A TGA dispersion test was performed under the same conditions as in Table 1.

Acid-functionalized polyamide (PA-COOH):
To obtain acid-functionalized polyamide (PA-COOH), 1550 g of isophorone diamine, 343 g of 2 methyl-1,5 pentanediamine, and 857 g of deionized water were added to a stirrer, nitrogen ejector, temperature control unit and distilled glass. It was placed in a 6 liter glass reactor equipped with a vessel. The reaction mixture was stirred until all components were dissolved. Upon dissolution, 2823 g of sebacic acid was added over 60 minutes to maintain the exothermic reaction below 80 ° C. After this addition, the mixture was slowly heated to 220 ° C. while distilling off water. After reaching the reaction temperature of 220 ° C., a sample for measuring the acid value and the amine value was taken every hour. After reaching the target acid value, the mixture was vacuum distilled for 30 minutes, then the vacuum was stopped and the resin was drained.
The molecular weight of the PA-COOH resin shown in Table 1 is 1800 Da to 15000 Da.

Sulfonate functionalized polyamide (PA-COOH-SO ₃ Na):
To obtain a sulfonate functionalized polyamide (PA-COOH-SO ₃ Na), 1550 g of isophorone diamine, 343 g of 2 methyl-1,5 pentane diamine, and 857 g of desalted water were added to a stirrer, nitrogen ejector, temperature control unit. And placed in a 6 liter glass reactor equipped with a diamine. The reaction mixture was stirred until all components were dissolved. At that time, 2786 g of sebacic acid and 47 g of 3,5 dicarboxybenzene sulfonate were added over 60 minutes to maintain the exothermic reaction below 80 ° C. After this addition, the mixture was slowly heated to 220 ° C. while distilling off water. After the reaction temperature reached 220 ° C., samples for acid value and amine value measurement were taken every hour. After reaching the target acid value, the mixture was vacuum distilled for 30 minutes, then the vacuum was stopped and the resin was discharged.

The molecular weight of the PA-COOH-SO ₃ Na resin shown in Table 2 is 1800 Da to 15000 Da.
NOVAMID® 2430A and NOVAMID® X21-F07 are polyamides that are not functionalized with carboxylic or sulfonic acid groups. These polyamides are commercially available from DSM.

Claims (15)

A film-forming dispersion containing functionalized polyamide and water.
The functionalized polyamide is a carboxyl compound functionalized polyamide and / or a sulfonate compound functionalized polyamide.
The functionalized polyamide reacts with at least one or more neutralizers in the presence of water, at least partially.
The proportion of the functionalized polymer in the solid content of the film-forming dispersion is at least 35% by weight, more preferably 50% by weight or more, still more preferably 45% by weight or more, based on the total solid content of the film-forming dispersion. A film-forming dispersion containing 75% by weight or more, most preferably 90% by weight or more. The neutralizing agent is preferably a base, more preferably selected from the group containing amines and / or inorganic hydroxides.
The amines are preferably secondary, tertiary or quaternary amines such as diethylethanolamine or trimethylamine and diethanolamine.
The film-forming dispersion according to claim 1, wherein the inorganic hydroxide is preferably, for example, sodium hydroxide or potassium hydroxide. Claim 1 or 2 is characterized in that the neutralization ratio is in the range of 100% or more and 400% or less, preferably 100% or more and 200% or less with respect to the acid functional value of the functionalized polyamide. The film-forming dispersion according to any one of. The functionalized polymer is functionalized with one or more linear dicarboxylic acids.
The film-forming dispersion according to any one of claims 1 to 3, wherein the linear dicarboxylic acid is preferably one or more selected from the group consisting of adipic acid, sebacic acid and isophthalic acid. The sulfonate compound comprises at least two carboxyl groups and at least one sulfonate group.
Preferably, the sulfonate compound contains an aromatic moiety, more preferably a dicarboxybenzene sulfonate, still more preferably a 3,5 dicarboxybenzene sulfonate, most preferably a 3,5 dicarboxybenzene sulfonic acid. The film-forming dispersion according to any one of claims 1 to 4, which is a sodium salt. The film forming according to any one of claims 1 to 5, wherein the functionalized polyamide has an acid value of 10 (mgKOH) / g or more and 100 (mgKOH) / g or less, which is determined by potentiometric titration according to ISO2114 (2000). Sex dispersion. The film-forming dispersion according to any one of claims 1 to 6, wherein the average particle size of the dispersed particles in the dispersion is 5 nm or more and 1000 nm or less, which is determined by a laser scattering method in distilled water. Further, the nonionic surfactant is contained in an amount of at least 1% by weight and up to 20% by weight, preferably 3% by weight to 15% by weight, and most preferably 5% by weight to 10% by weight, based on the weight of the functionalized polyamide. , The film-forming dispersion according to any one of claims 1 to 7. The film-forming dispersion according to any one of claims 1 to 8, wherein the film-forming dispersion is essentially free of catalyst and / or substantially free of solvent. The weight loss of the functionalized polyamide is 15% or less, preferably 10% or less, more preferably 8% or less, and the weight loss is determined by thermogravimetric analysis at 350 ° C. in an air atmosphere in a closed oven. The film-forming dispersion according to any one of claims 1 to 9, which is a weight loss when heated from 50 ° C. to 400 ° C. for 70 minutes using 15 mg of functionalized polyamide as a starting material. The film-forming dispersion liquid according to any one of claims 1 to 10, wherein the film-forming dispersion liquid is a dispersion liquid in which particles are dispersed in a liquid phase. Fibers, preferably carbon fibers treated with the film-forming dispersion according to any one of claims 1-11;
A composition comprising a resin, preferably a thermoplastic resin. It is a manufacturing method of fiber reinforced plastic articles.
The process of providing fibers, preferably carbon fibers;
The step of treating the fiber with the film-forming dispersion liquid according to any one of claims 1 to 11 to obtain the treated fiber; and the step of applying the resin to the treated fiber. A method for manufacturing a fiber reinforced resin article containing. A fiber-reinforced article containing fibers, preferably carbon fibers treated with the film-forming dispersion according to any one of claims 1 to 11, and a resin. Use of a film-forming dispersion using the film-forming dispersion according to any one of claims 1 to 11 as a film-forming agent for fibers, preferably carbon fibers.